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ATMOSPHERIC ENVIRONMENT · 2023 · IF 5

Influence of temperature on the heterogeneous reaction of toluene to N-containing organic compounds using in situ DRIFTS

Xiang He,Aiyilaiti Kudesi,Shuangxi Wang,Xin Liu,Lin Hu

Heterogeneous reactions of toluene/NO 2 with and without O 3 on α-Fe 2 O 3 particles was studied as a function of temperature by using in situ diffuse reflectance infrared Fourier transform spectrometry (DRIFTS). The results show that the formation of R-ONO 2 group is identified on the α-Fe 2 O 3 particles surface, indicating the formation of benzyl nitrate in the presence of toluene/NO 2 with or without O 3 at different temperatures from 253 K to 298 K. From the analysis of the spectral changes, the reaction kinetics, such as reaction rate and uptake coefficient are sensitive to temperature. During the heterogeneous reaction of toluene/NO 2 , the formation rate of organic nitrate increases from (2.38 ± 0.07) × 10 17 ions g −1 s −1 to (5.95 ± 0.09) × 10 17 ions g −1 s −1 when the temperature decreases from 278 K to 253 K. When the trace gases were toluene/NO 2 /O 3 , the reaction rate increases about 3 folds with the increasing of temperature from 253 K to 298 K. In the absence of ozone, nitrification from heterogeneous reaction is exothermic process. However, the addition of ozone dominates the whole reaction process, resulting the different change trends of formation rate at similar range of temperatures. Furthermore, reactive uptake coefficient increases from (6.73 ± 0.02) × 10 −7 to (1.64 ± 0.05) × 10 −6 with decreasing temperature from 278 K to 253 K during the heterogeneous reaction of toluene/NO 2 on α-Fe 2 O 3 particles. The values of activation energy for the heterogeneous reaction of toluene/NO 2 and toluene/NO 2 /O 3 are determined to be −8.60 ± 0.91 kJ mol −1 and 15.14 ± 2.51 kJ mol −1 , respectively. It implies that the heat change is an important factor in affecting the heterogeneous reaction under the seasonal temperature changes.

CAS / MDL: 1309-37-1
研究领域: 大气化学 · 环境科学
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JOURNAL OF FORENSIC SCIENCES · 2020 ·Vol. 65 ·期 3 ·1016-1022 · IF 1.441

Fatal Methemoglobinemia Due to Acute Inhalation of Methyl Nitrite in an Industrial Accident

Sizhe Huang,Rongshuai Wang,Bingbing Guo,Hongbin Ruan,Jinghong Ma,Liang Ren,Liang Liu

Methyl nitrite is suggested to cause methemoglobinemia by generating methemoglobin, which may be lethal when the methemoglobin concentration exceeds 70%. However, intoxication with methyl nitrite is seldom reported compared with that with other nitrites. Here, we present an industrial accident involving methyl nitrite inhalation during its synthesis process that resulted in three fatalities and one survivor. The autopsy revealed conspicuous blue-gray discoloration in various parts of the body, including the skin, airway mucosa, vessels, brain, heart, and among other areas. The toxicological tests on the deceased showed methemoglobin concentrations in the blood over the lethal level and increased nitrite ion levels in the blood, gastric contents, liver, and lung tissue compared with those in control samples. The cause of death was determined to be methemoglobinemia-induced hypoxia due to methyl nitrite inhalation. This report provides evidence that in methyl nitrite intoxication, exposure duration has a significant influence on the postmortem changes and likelihood of a fatal outcome may be related to the age of the victim. More attention is required regarding the industrial hazards of this substance.

研究领域: 法医学 · 毒理学 · 职业健康
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RESEARCH ON CHEMICAL INTERMEDIATES · 2015 ·Vol. 42 ·期 3 ·2211-2220 · IF 1.221

A simple and efficient approach for highly selective preparation of nitrocyclohexane from cyclohexane with tert-butyl nitrite catalyzed by N-hydroxyphthalimide

Liu Shuilin,You Kuiyi,Jian Jian,Luo Qing,Liu Pingle,Ai Qiuhong,Luo He’an

A simple and effective approach for highly selective preparation of nitrocyclohexane from cyclohexane using tert-butyl nitrite as a nitrating agent under atmospheric pressure has been successfully developed in this work. The results indicate that the N -hydroxyphthalimide catalyst gave the best results with 27.3 % of cyclohexane conversion and 88.0 % of selectivity to nitrocyclohexane under optimal reaction conditions. The present reaction provides a novel strategy for the synthesis of nitroalkanes from the nitration of low-carbon alkanes because of the mild reaction condition, simple experimental procedure and high selectivity towards the desired product. This method may be very significant to establish such a synthesis method for aliphatic nitro-compounds from the low-carbon alkanes in organic fields.

研究领域: 有机化学 · 合成化学
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CATALYSIS LETTERS · 2025 ·Vol. 155 ·期 10 ·1-12 · IF 2.4

Impact of Water Content on UiO-66 Synthesis and Catalyst Activation in Pd/UiO-66 Catalyzed Methyl Nitrite Carbonylation to Dimethyl Carbonate

Huang Qiuyun,Liu Shiyu,Shen Weihua,Fang Yunjin

Due to the modifiable properties and excellent stability, metal-organic frameworks (MOFs) are considered potential catalyst supports in heterogeneous reactions. UiO-66 with varying water contents were synthesized as supports of Pd for the carbonylation of methyl nitrite (MN) to dimethyl carbonate (DMC). In accordance with XRD, NH 3 -TPD, and SEM, the water contents showed a negative correlation on the amounts of acid sites and accelerated crystal aggregation. The Pd/UiO-66(x) demonstrated perfect selectivity of DMC (> 99%) and good CO conversion which were increased with the decrease of water contents. Moreover, the catalysts deactivated at the beginning of the reaction, and the catalytic deactivation was due to the damage of the C = O structure in UiO-66 frameworks. This work revealed the influence of water contents on the synthesis of UiO-66 and the deactivation process of MOF-based catalysts in MN carbonylation to DMC. Graphical

研究领域: 材料化学 · 催化化学 · 无机化学 · 多孔材料 · 工业催化
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BIOMATERIALS · 2019 · IF 10.273

A pH/Ultrasound dual-response biomimetic nanoplatform for nitric oxide gas-sonodynamic combined therapy and repeated ultrasound for relieving hypoxia

Jie An,Yong-Guo Hu,Cheng Li,Xiao-Lin Hou,Kai Cheng,Bin Zhang,Ruo-Yun Zhang,Dong-Yu Li,Shao-Jun Liu,Bo Liu,Dan Zhu,Yuan-Di Zhao

Sonodynamic therapy (SDT) has rapidly developed as a powerful alternative to traditional photodynamic therapy due to its intrinsically deeper tissue-penetration. However, single SDT dose is incapable of radical cure because the long-term hypoxia of tumor limits its therapeutic effect. Herein, we developed a biomimetic nanoplatform with dual pH/ultrasound response, homologous targeting and low phototoxicity for combined nitric oxide (NO) gas therapy with SDT to solve the problem. This nanoplatform is composed of zeolite imidazole framework-8 material embedded with nitrosoglutathione (GSNO) and chlorin e6 (Ce6) by one-step encapsulation, and then wrapped by homologous tumor cell membrane . In vitro and in vivo experiments indicate that the biomimetic nanoplatform has excellent biocompatibility and shows higher retention in tumor by homologous targeting. Importantly, it can sustainably release the encapsulated drug in acidic tumor microenvironment and accelerate degradation by ultrasound (US). Furthermore, NO released from GSNO and reactive oxygen species generated by Ce6, which are both triggered by US, react with each other to produce highly reactive peroxynitrite to inhibit the growth of tumor. Moreover, by repeated US irradiation, the tumor hypoxia can be relieved for a much-longer term, resulting in an effective gas-sonodynamic combined treatment. This study fully utilizes the advantages of US, providing a new strategy for high-performance cancer therapy.

研究领域: 癌症治疗 · 纳米医学 · 生物医学工程 · 药剂学
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Materials Today Nano · 2024 · IF 8.2

A highly permeable nanoplatform based on functionalized carbon dots for synergistic reactive oxygen/nitrogen species tumor therapy

Jiangyong Li,Qin Li,Qian Yang,Qi Tang,Xiaoyi Hu,Qing Liu,Liangke Zhang

Reactive oxygen species (ROS)-based antitumor strategies, particularly chemodynamic therapy, have garnered considerable attention. However, challenges such as difficulties in achieving deep penetration, relatively low H 2 O 2 levels in the tumor microenvironment, the requirement for low pH by the Fenton reaction, and their short lifespan have impeded satisfactory therapeutic outcomes. Hence, we have developed a nanoplatform with enhanced permeability that not only generates significant amounts of ROS but also converts them into longer-lasting reactive nitrogen species (RNS), thereby improving tumor therapy efficacy. In our study, carbon dots were functionalized by doping with gold atoms and grafting nitrosoglutathione (GSNO) to form ACN, which exhibits glucose oxidase-like properties and enables laser-responsive NO release. ACN and indocyanine green (ICG) were then loaded onto MnO 2 nanoflowers to form MnO 2 @AI. Upon arrival at the tumor site, MnO 2 reacts with H 2 O 2 and GSH, leading to its degradation and the subsequent release of ACN, which is characterized by three permeation-promoting properties: ultra-small size, positive charge, and NO content. In addition, ACN promotes H 2 O 2 production through glucose metabolism and reduces pH, both of which enhance the Fenton-like reaction of MnO 2 , thereby amplifying ROS generation. The ICG in MnO 2 @AI enhances its photothermal properties, leading to the responsive release of NO from GSNO grafted onto ACN, which then reacts with the increased ROS to generate more toxic RNS. Collectively, the approach described herein offers substantial potential for advancing the treatment of malignant tumors.

研究领域: 纳米技术 · 癌症治疗 · 材料科学 · 生物医学工程
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